Copolymerization of diolefins and aromatics



logues.

Patented Jan. 6, 1953 COPOLYIVIERIZATION OF DIOLEFINS AND AROMATICS George E. Serniuk, Roselle, N. J., assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application December 2, 1949, Serial No. 130,847

18 Claims. 1

This invention relates to the manufacture of resinous masses and more particularly relates to the preparation of resins by the copolymerization of diolefins and aromatic hydrocarbons.

The reaction of conjugated dienes and aromatic hydrocarbons to form resinous bodies has been known for some time. See, for example, U. S. Patent No. 1,947,626 to Charles A. Thomas, and Industrial and Engineering Chemistry, vol. 24, pages 1125-8 (1932) According to the method disclosed in these references, the resins are prepared by the application of solid aluminum chloride or other solid acid-acting halide catalyst to the hydrocarbon mixture at temperatures of 20 C. or above. However, the product is disclosed as containing a substantial amount of insoluble material. Furthermore, the process is limited to the use of substituted benzenes as the aromatic constituent, since benzene itself does not react under these conditions.

It has now been found that essentially gel-free (i. e, free from insoluble material) resinous polymers of varying softening point and degree of unsaturation can be prepared in high yield at fairly high catalyst efliciencies from diolefins and aromatic hydrocarbons, including benzene, by effecting the reaction at temperatures below C. using a dissolved Friedel-Crafts type catalyst.

In carrying out this invention, various diolefins may be used with various aromatic hydrocarbons free from olefinic unsaturation. For example, very satisfactory results have been secured by using a diolefin, such as isoprene, with benzene, toluene, or the xylenes, or their homo- Other aromatic hydrocarbons have been found to give good results, such as ortho, meta and para xylene, cymene (methyl isopropyl benzene), ethyl benzene, di-ethyl benzene, normalpropyl benzene and isopropyl benzene, tetra-.

methyl benzene, secondary butyl benzene, tertiary butyl benzene, amyl benzene, tertiary amyl benzene, hexa-methyl benzene, mesitylene, durene, isodurene, phenanthrene, enthracene, tetralin, hydrindene, as well as various petroleum and coal tar fractions containing these. Particuularly interesting resins are obtained when the aromatic hydrocarbon is substituted by one or more alkyl side chains containing a total of at least one, preferably at least three and up to six, carbon atoms. For example, ethyl-, diethyl-, and triethyl-benzene, alkylated naphthalene and durene give resins which posses excellent drying properties. Other conjugated diolefins oi 4 to 6 carbon atoms may be used, such as the hexadienes, butadiene, di-methyl butadiene, methylpentadiene, cyclopentadiene, methylcyclopentadiene, as well as allo-ocimene, myrcene, etc.

When employing alkylated aromatics, such as toluene, xylene, etc., as the aromatic constituent, it may be desirable to carry out the process of the present invention in two steps, in the first of which an aromatic hydrocarbon is alkylated and, in the second, in which the product is copolymerized with the diolefin.

In the first step, an aromatic such as benzene, toluene, xylene, naphthalene, anthracene, etc., is mixed with a Friedel-Crafts catalyst such as AlCls, A1Bl'3, SnClr, ZnClz, BF3, etc., in a diluent such as methyl chloride, ethyl chloride, methylene chloride, ethylidene fluoride, etc., and to this is then added an olefin such as ethylene, propylene, butene, isobutene, amylene, or a mixture of olefins, such as are found in refinery streams of C4 and C5 cuts. The olefins are added to the system as rapidly as they can be reacted with the aromatic to form the alkyl aromatic. For example, benzene may be reacted with propylene to form mono, di, tri or tetra isopropyl benzene, or mixtures thereof. Toluene may be reacted with propylene to form monoor poly-isopropyl toluene, etc. The alkylation of the aromatic by the olefin may also be accomplished in the presence of activated clays.

The second step consists of adding the desired amount of butadiene or other conjugated diene to the alkylated aromatic produced, mixing in a diluent system, and then adding additional catalyst (AlCls in ethyl chloride) to effect a simultaneous alkylation and polymerization of the feed to polymer. The conjugated dien and alkylated aromatic can be polymerized in varying ratios, however, ratios of 50/50, 55/45, 60/40'and /35, /25, respectively, are preferred. In some instances it may be advantageous to separate specific alkylate cuts prior to the addition of the diene in order to obtain the desired physical properties. For example, it may be desired to use the cli-allgvl aromatic in which case this material would be separated from any mono or higher substituted alkyl aromatic, and the mono-alkyl aromatic could be recycled for further alkylation.

The characteristics and yields of the resins that can be produced by this process are dependent upon the type of diene and aromatic, ratio of diene to aromatic in the feed, and the type and amount of catalyst employed, and the reaction temperature. By employing a major proportion of a diene and a minor proportion of an aromatic the resultant polymers are generally more unsaturated and the yields are higher than when the converse ratios are used. Thus the amount of diene combined in the product, and conse: quently the degree of polymer unsaturation can be varied by adjusting the ratio of diene to aromatic in the feed.

Resinous products with desirable properties can also be prepared by using a mixture of dienes and a single aromatic or a mixture of aromatics.

In practicing the invention the two components.

i. e. the dlolefln and the aromatic hydrocarbon, are mixed and cooled to temperatures below 0., e. g. about l0 C. to as low as 40 C. or -50 C. or even as low as -100 C. or -l50 C.

The polymerization reaction is then conducted by the application of a dissolved Friedel-Crafts type catalyst, such as aluminum chloride, aluminum bromide, titanium tetrachloride, boron trifiuoride, uranium chloride and the like, dissolved in a low-freezing, inert or non-complex forming solvent, such as .ethyl or methyl chloride or carbon disulflde or the like. The catalyst solution contains from 0.1% to 5% or preferably 2 to 3.5% of the dissolved active metal halide catalyst and is preferably used in the ratio of about parts per 100 parts of the dlolefln. The polymerization proceeds promptly with the development of a substantial amount of heat and the production of a soluble polymer in the form of a solution.

By effecting the reaction in this manner, there are produced several products: (1) resinous polybenzene, toluene and xylene and similar alkyl benzenes, it is possible to obtain fair yields of polymer when reacted with butadiene in a .high ratio. However, the resin yields pass through a maximum value for the respective aromatics and the remainder of the product formed being an aromatic-diene alkylate of low molecular weight.

In order to reduce the amount of low molecular weight alkylate formed, it may be desirable to introduce the diolefln incrementally to react with this alkylate. In this case the catalyst is also added incrementally. In this embodiment the initial feed consists of a major proportion of the aromatic and a minor proportion of the diene. For maximum resin yields, a diene to aromatic ratio of 60/40 is preferred, but with certain types of aromatics higher diolefln ratios live It may also, under certain circumstances, be desirable to isolate the alkyl aromatic and then react it with the dlolefln under the same conditions used in the original reaction. These alkyl aromatics generally distill over at a temperature range of 130 C. at atmospheric pressure to 196 to 200 C. at 5 mm. of mercury. The product can therefore be distilled under these conditions and then reacted with more diolefln.

The following examples are set forth to illustrate the types of products that can be obtained by the process of this invention.

EXALEPLE I Polymers of butadiene and benzene were prepared from varying feed ratios of butadiene and benzene in the following manner: a 5-liter 3-way flask, fitted with an air driven mechanical stirrer, Dry-Ice cooled reflux condenser, thermometer and catalyst delivery funnel, was charged with methyl chloride (amount of methyl chloride equaled one-half of total volume-of reactants) and the desired amounts of butadiene and benzene (total weight was generally 750 g.). The mixture of butadiene, benzene and methyl chloride was then agitated until an equilibrium temperature was reached. Aluminum chloride (anhydrous) dissolved in ethyl chloride (concentration of A101: was generally 2 to 3.5 g./l00 cc. ethyl chloride) was then added in increments to the reaction charge.

The rate at which the catalyst solution was added was governed by the activity of the reaction. The amount of catalyst that was delivered was based on the observation of a diminished reactivity and volume of reflux of the methyl chloride. when a diminished reactivity was ob- The methyl and ethyl chlorides were allowed to a served a 15 minute contact period was allowed following the addition of the last portion of catalyst solution. The catalyst was then quenched with a mixture of isopropyl alcohol and water.

higher resin yields. The following data were obtained:

' TABLE I Mine-beau" polymer:

Experiment No a B o n a r a Butadiens, g. 160 coo Ratio NHL--- Diluent: M201 Vo EI'EIII as:

Percent total feed vol GL5-.. Catalyst:

Bolv t lttCl.---

Cone, g./l00 cc 3.12.-.

Solution used, as am Percent on feed.. 1.250.--.

Eiilciency l9.9.-.-. Reaction:

Time, mln W Temp., -10 to Reoove Pr uct, g- 18 Yield, percent on total... 25

Yicetld, permit on diene 124 8-poiymsr retained in solution.

2,824,726 5 6 EXAMPLE 2 Polymers of butadiene and toluene were Drepared according to Example 1 and the following data were obtained: v

TABLE 11 Mime-toluene polymer:

Experiment No A n I c n E F o n Butadiene,g I 625"..- 600 675.

Pr uct, g

Yield, percent on total Yield, percent on diene Product:

Color Salt. pt.

Iodine o B-solt; H-hard; A-amben-L. A.light amber.

Polymers of butadiene and xylene were prepared according to the process of Example 1 and the following data. obtained:

TABLE III Butadiene-nlme polymer:

Experiment No .L A. B O D E l F G Butadiene, g 150 226 300 376 450 62b-.- Xylene, g 625 450 375 225 60 Ratio 30/70.--. Diiuent:

e Vo 0c Percent total feed vol Catalyst:

T AiOh-.. A101:

Reeove Pr not, g Yield, percent on totaL. Yield, percent on m oduct:

F-fluid; S. B.semi-eolid; D. A.-dark amber; B-reddish; L-llzht EXAMPLE! trieth l benzene were re red according Polymers of butadiene and ethyl, diethyl and y p pa in the 9,694,796 7 process of Example 1 and the foliowins date were obtained;

TABLE IV Butodkae-ethflded beam polymer D E F G McCl..- MeCl. 150...-.. 150.--.-. 1m.

AlCh.-- M011... M011... A1011.-- A1013..- A101... A101.

EtCL.-. EtCl.-.- EtCL-.- EtCL--. EtCl. 3.47"..- 3.78- 3 3.47.

In Time, min Temp., C

V. L-vilooul fluid; 8. Broom-solid; R-reddish; A-ember; D. A.-dark ember.

EXAMPLE 5 to prepare polymers from butadiene and a 90% 5 pure durene. The results are tabulated below: Polymers of butadiene and naphthalene were prepared according to the process of Example 1 I TABLE VI and. the following data. were obtained:

Butadime-durme polymen Butadiene-naphthalene polymer Experiment No A B C .D TABLE V Butodlmema hihalene mer 300 P PM 200 n m Experiment No A B 0 $01...

Buiadiene, g Nephthnlene, 3. Ratio Vo fi cc Percent total feed vo. nteiyst: Efficiency Type. AlCh.... AlCh.... AlCh. Reaction: Solve EtCl.. :01.-.. EtCl. 'lime,min 80 91 o0 00. Conc.,g/1 4.88..... 3.84..... 3.52. Temp.,C l7.5to i7 to 17 to -15. S0] used, 1.0%.... 1,000.--. 700. i3.5. 155 i4.

48.8"... 38.4..... 24.6. Recovery: eroenton (eed..... 6.45..." 5.1 3.28. Polymeng 447 490 459 o.

Emcieney 12.8... 17.7..... 33.4. Conv.,peroent 89 98 92 93.5.

iun; Product:

State Soit..... Soft"... Soit.... 78.5C. Color Amber Reddish. Amber Amber. 0 Iodine N0 149 6.7.... 163 136.8.

EXALEPLE'I A polymer of 1,3-butadiene and benzene was prepared in the following manner: A 5-liter 3- EXAMPLE 3 way round bottom flask fitted with a mechanical stirrer, Dry-Ice cooled reflux condenser, ther- The procedure described in Exampie 1 was used mometer and catalyst delivery tunnel was charged with 552 cc. of methyl chloride, 338 g. of benzene and 114 g. of 1,3-butadiene. The materials were well agitated and when equilibrium temperature was reached AlCl3 catalyst dissolved in ethyl chloride, concentration of 3.6 g. A1C13/100 cc. ethyl chloride, was added in increments- Three hundred grams of 1,3-butadiene were added in three equal portions at various times during the course of the polymerization as indicated by the log of the reaction given below:

1 Vo l. emp. ca Time O SOL, Remarks :00:00" 13'5 50 Reactive foamy reflux, color change to gfgfgg" 0 dark re'ddish, vigorous reflux upon addg $3 0 ing catalyst.

f f 100 g. 1,3-butadiene added foamy reflux 3 1 150 reactive, dark red color, still active re: 0.23.25" l2.0 flu 0:25:00 200 0:38:38 l2.0 0. a A

j I 100 g. l-3-butadiene added foamy, re- 3:23:82 I active, darker color.

0:39:00; 300 }Vigorous reflux, reactive, some viscosity gfiiskgfl -11.0 build up.

f 100 g. 1,3-butadiene added reactive, 813193" a-3' foamy, viscous, dark color.

0:575:30: Catalyst quenched with 100 cc. of methanol, 1,000 cc. 54 naphtha added.

The polymer solution was allowed to stand at room temperature to weather off methyl and ethyl chlorides. The reactor solution was poured gradually into a large volume of 99% isopropyl alcohol whereupon the polymer precipitated out as a resinous body. The polymer was freed of moisture and solvents by heating at 85 C. in a vacuum oven. There were obtained 355.5 grams of a light colored, brittle resin which corresponds to a 47% conversion. A similar reaction effected with all of the butadiene added initially resulted in a 35.5% conversion to soft polymer.

EXAMPLE 8 A 5-liter 3-way flask fitted with a mechanical stirrer, Dry Ice cooled reflux condenser, catalyst delivery tube and thermometer was charged with the following: toluene, 500 g.; 1,3-butadiene, 500 g.; methyl chloride, 750 cc. To the above was delivered 1075 cc. of an ethyl chloride solution of anhydrous alminum chloride containing 3.76 g. of AlCh/lOO cc. of solution over a period of one hour and fifty minutes. After two hours and five minutes the catalyst was quenched with methanol (150 00.). The methyl and ethyl chlorides were flashed off and the resin solubilized in n-heptane. The catalyst residues were removed by water washing. Solvents were stripped under desk vacuum. The unreacted materials were removed by distillation at 5 in. m. p. at a bottoms temperature of 260 C. There were recovered 681 g. of a clear, light colored, soluble resin possessing a ball and ring softening point of 100 C., and an iodine number of 88.

EXAMPLE 9 Equipment described in Example 8 was charged with the following: xylene, 500 g.; 1,3-butadiene, 500 g.; methyl chloride 740 cc. To the above was delivered over a period of one hour and fifty minutes a total of 810 cc. of an ethyl chloride solution of anhydrous aluminum chloride containing 3'72 g. of AlClz/lOO cc. of solution. The reaction mixture was then allowed to stand over night without quenching the catalyst. On the following day the reaction mixture was heated oin a water bath at 80 C. for 4 hours thereby distilling off methyl and ethyl chlorides. The reaction product was solubilized in n-heptane, and the catalyst quenched with 150 cc. of methanol. The product henceforth was'isolated in the man ner disclosed in Example 8. There were recovered 795 g. of clear, dark amber colored, soluble resin possessing an iodine number of '72 and a ball and ring softening point of 123 C.

EXAMPLE l0 Attempts to prepare a completely soluble, high melting point resin, by the technique disclosed in the prior art, resulted in a low conversion of the feed to a product consisting of a minor proportion of a soluble polymer and a major propor- EXAIVIPLE 11 A 5-liter 3-way flask fitted with a mechanical stirrer, Dry-Ice cooled reflux condenser, thermometer and catalyst delivery funnel was charged with the following: methyl chloride, 740 cc.; 1,3- butadlene, 500 g.; toluene, 500 g. The charge was agitated until equilibrium temperature was reached. An ethyl chloride solution of anhydrous aluminum chloride. containing 3.4 g. aluminum chloride/ cc., was added in increments to the reaction charge. A total of 1177 cc. of catalyst solution, equivalent to 40 g. of aluminum chloride,

was added over a period of one hour and fifty I minutes. At the end of two hours the catalyst was quenched by the addition of 150 cc. of

methanol. The solution was allowed to stand to weather off methyl and ethyl chlorides. The product was diluted with petroleum ether. The

alkenyl aromatics and resin were isolated in the following manner: The entire solution was subjected to a distillation in which the petroleum ether was taken off at a vapor temperature of 75 C'., and following this the fractions listed below were collected:

1st fraction, B. P. 75-115 C., 140 g.

2nd fraction, B. P. -135 C., 45 g.

3rd fraction, B. P. 80-90 C. (5 m. m. p.) 58.9 g. 4th fraction, B. P. 95140 C. (5 m. m. p.), 26.6 g. 5th fraction, B. P. -18'7 C (5 m. m. p.), 25.3 g. Toluene and alkenyl aromatics, 296 g.

or 29.6% based on the feed. Resin obtained as residue of distillation-670 g. or 67% conversion based on the feed.

Two such runs Were made from which a total of 596 g. of toluene and alkenyl aromatics with the above boiling range were collected.

EXAMPLE 12 The recovered toluene and alkenyl aromatics described in Example 11 were reacted with a fresh charge of butadiene. The apparatus was the same as that described in Example 11 and the charge was as follows: methyl chloride, 740 cc.; 1,3-butadiene, 500 g.; recovered toluene and alkenyl aromatics described in Example 11, 500 g.

a,sa 4,7as

ride/100 cc. ethyl chloride over a period of one hour and 54 minutes. At the end of two hours and minutes the catalyst was quenched with 150 cc. of methanol. the same as described in Example 11. A total of 590 g. of a clear, light colored, hard, brittle resin was obtained. It is clear from this experiment that the recovered aromatics and alkenyl aromatics described in Example 11 can be reacted with additional butadiene to produce a useful The polymer recovery was i 12 described in Example 11. The above fractions of alkenyl aromatics singly or combined or admixed with alkylated aromatics are equally well suited for reacting with additional 1,3-dienes to form resins according to the procedure described in Example 12.

' EXAMPLE 14 Polymers of butadlene and aromatic petroleum fractions were prepared in the equipment of Example 8 from varying feed ratios using methyl chloride diluent and a catalyst consisting of aluminum chloride dissolved in ethyl chloride.

resin by employing the same reaction conditions The following data were obtained:

Tasha vrr Polymer synthesis Polymer properties Ratio no (llatta- (gatiz- Poly- 801- loan] Beac n ys ys mer toning s Aromatic temp., O. percent e conv., Color L, No.

A ti iracti B.'P., 157-185 C 55 45 mum c on 60/40 l6 to l4.. 1. 78 48. 7 40/00 15 to 12.5.. 1. 52 40. 5 50/50 -15 to 12.5 3. 33 22. 2 Aromatic fraction, 3. P., 192-318 C 60/40 14 to 12 2. 56 31.] 70/30 14 to 13. 1.28 39.4 80/2) l5 0. 8 54. 3 50/50 1. 56 31. 6 Aromatic fraction, 13. P., 195-189 C 55/45 16 to 14 2. 23 29. 7 60/40 l5 to -13 2. 21 34. 4 50/50 15 to 13.5 2. 24. 7 Isodurene fraction 55/45 15.5 to l3 2. 35 2s. 2 60/40 -15.5 to i-li 2.35 Prehnitene fraction Z313 Z1228 I ,11 g; 6

used in the preparation of the resin described in Example 11.

EXAMPLE 1a Alkenyl aromatics of the type described in Example 11 do not necessarily have to be produced by the reaction therein described. Alkenyl aromatics of this type can be deliberately prepared by reacting a 1,3-diene and an aromatic in the presence of an ethyl ether or beta, beta-primedichloro ethyl ether complex of aluminum chloride. The preparation of alkenyl aromatics is described below. The apparatus of Example 11 was charged with the following: toluene, 920 g.; 1,3-butadiene, 108 g. To the above was added in increments over a period of one hour and thirtytwo minutes a complex formed between 66 g. of aluminum chloride and 74 g. of anhydrous ethyl ether. As the final portion of the catalyst was added the reaction became quite exothermic. At the end of the exothermic reaction the catalyst was quenched with 150 cc. of methanol. The catalyst residues were removed by water washing. The solution was dried over sodium sulfate and filtered. The filtrate was then subjected to distillation and the following fractions were collected:

1st fraction, B. P. 130-140 C., 60.6 g. or 22.2%

2nd fraction, B. P. 140-180" 0. 9.1 g. or 3.3%

3rd fraction, B. P. 180205 C., 17.4 g. or 6.4%

4th fraction, B. P. 170-190 C., 95.5 g. or 35.0%,

desk vac.

5th fraction, B. P. 110l96 C., 39.4 g. or 14.4%,

5m. m. p.

Residue, B. P. 196 C. at 5 m. m. p., 59.7 g. or 18.6%.

All of the above fractions rapidly decolorized an acetone solution of KMnOr. The above fractions of alkenyl aromatics show almost the same boiling range as those isolated from the resin reaction The resins prepared in accordance with the invention are found to have an amber to reddish color and to find application in the surface coating field, either as such, or after reacting with natural drying oils, in printing inks, rust preventatives, can coatings, leather treatment, rubber plasticizers, etc. In making the coating material the resin is placed with the desired drying oil or combination of oils in a suitable vessel and heated to 250 to 565 F. The heating is continued until the combination of oil or oils and resin have acquired a satisfactory body" or degree of consistency. This is Judged by the appearance and by other characteristics and tests generally employed in the bodying step in varnish making. For a mixture of about 100 g. about one hour is required for heating, when the usual "body is desired; but the exact time of heating will vary with the volume of the mix, the nature of the resin and the oil and the consistency desired. The properly heated mixture is allowed to cool, then thinned with a varnish thinner such as mineral spirits, to obtain'the desired viscosity. Instead of varnish thinners. cheap thirmers, such as gasoline or naphtha, may be used, as this resin. as well as the reaction product of this resin and oil, have the unusual property of being sufllciently soluble in relatively cheap solvents, such as gasoline or naphtha, to produce a coating material or varnish of proper consistency for application as a protective coating.

The coating material described, with or without pigments or metallic driers, and using a usual paint or varnish solvent or a relatively cheap thinner, such as gasoline, produces a film which, when baked at C. for one hour, is relatively insoluble in gasoline and paint and varnish solvents. That is, the film remains unaflected by immersion in gasoline or other organic solvents for one hour or longer. When the film is air 13 dried at room temperature for several days, it likewise becomes relatively insoluble in gasoline and other organic solvents in the manner described above. The filmthus formed is also impervious to water and very resistant to acids and alkalies.

The dried film produced from this coating material made from a reaction product of the described resin with a drying oil, has also the very, desirable property of high elasticity or flexibility. That is, the film will withstand a high degree of stress and shock without cracking, peeling, chipping or otherwise being injured. This property tion product of the described resin with a drying oil.

The following examples are illustrative of the type of films and coatings obtained by the process of this invention.

EXANLPLE 15 The resins obtained in Examples 1-6 were reacted with alkali refined linseed oil to give a 15 gallon length varnish. The varnishes were diluted with naphtha, conventional driers added, and panels were prepared. The air dried and baked film properties were then evaluated and of high flexibility characterizes the novel reacthe results shown in the following tables.

TABLE VIII Butadiene-benzene polymer-linseed oil varnishes Experiment N A Y B C D E F G esin:

OAHQ/CIHQ ratio in feed 80/2). Percent dieue in product Varnish preparation:

Cook time, hrs.: min. ('0. F 400.

13.6 -I 10.6 0. Naphtha. Naphtha. Nephtha. Naphths. Naphtha. Naphtha. Naphtlm.

oansa: roaaoqanc .esmsa: -x=a zme waaaao: naouau :A

PPPPP? $992M? g e Time required to reach cook tern indicated, ca. hour. 5 Complete gel. Panels could not e prepared.

@ Varnish was stringy and gelatinous.

TABLE Ix Butadime-toluene polymer-linseed oil varnishes Experiment No. A B C D E F G E as /80...-. l70-..... /60"-.- /50--... /40..." /30..... /20".-- /10. Perc'ent diene in prod- 4s 51 57. s 65 71 09. n 92. s Varnish preparation:

Cook time, hrs.:min 5:00 5:35 4:45 2:40 4:05 2:18 5:30 4:00.

Percentbase loss 24.2 18.2 21. 15.2 10. 9.1 Thinner Naphtha. Naphtha. Naphtha. Nephtha. Naphtha. Nephtha. Naphtha. 'Naphtha.

Color 10-11-- 16-17..--. 16-11..-- l5-10- 11-l2 10-11 10-11 10- Viscosity P S U V X Y K-L K-L Airdried fllm Hardness 0- 0..

Water re i tnnna 0 0 Grease resistance- Warnish cook temp. was 500F. Others were 565F. o-iilm unaflected; 9-fiim isllure.

TABLE X Mime-xylem pol uhllmad bil lamialm Experiment No A B C D E F G Resin:

CHl/ClH|(CHl)imtlinieed so.-.-- /70..... 40/00..... 50/50..... 00/40..." 7o/ao.... aom. Percent dieneinproduct M 49 76 90.

(-) x W- UV-.... I

L 1 n 1 2 0 T. 8 Water resistance... 0 0 0 0 7 Grease resis R 7 n n a Caustic rmiitanm 2 4 6 6 7 Flex resistance.. 0 O 0. n n Boa mjginnm O 5 6 5 8 'Baked 1m":

Hardn 1 0 1 n 0. 0. Water r 0 0 0 0 0. G ease aminar-am 0 0 n 0. n 2. Caustic resistancen n 1 4 1 Flex resistance.. 0 0 0 n 0 0. Soapresistance.. 4 4 2 0.

l Varnish gelled. b 0-fllm uuaflectcd; 9-fllm iailure. '1. B.fl1m was too soit.

TABLE XIII I Bumdienmphthalenc pol men-Summary of linseed a vanmh lll properties 30 TABLE XI Experiment No A c Bundle-n: and ethulaud bmmus-linued oil varniahu Resin-CdL/CuHa ratio in feed.. Erp riment No E F G Vengfihtpreparation:

y Varnish preparation:

Cook time, hrs; min 3:00 3:27 4:40. Base loss, percent...- 13.2 12.6.".-. 11.5. Thinner Naphtha. Naphtha. Naphtha. Gardner:

Color 3 11-12".-- 11-12. Viscosity" UV---- U-V--- V-W. I 40 Reduced cure 26.. 18 15. Air dried film Air dried film Hardness Hardness. Water resistance.. Water resistance Grease resistance.-- 7 Grease resistance Caustic resistance 7 Caustic resistance. Flex resis Flex resistance... Soap resistance Soap resistance" Baked flim Hardneu Water resistnnm I O-illm unaffected; 9-illm failure. Grease resistance Caustic re istance Flex rpni mnm Soap resistance I 0-Film unaflccted; 9 nlm failure.

TABLE III Film property ratings of ethyl, did"! and kidhflbmum-buadiene polymer:

Film air dried, 2% Film air dried, 11% to B k days 12 days 5 ed mm Experiment No. Samples woscnr'rwusonr'rwcsonr'r O|H lEtPhrstio20/B0 .---0D0010349000040911043 C HJEt2Phratio20/80.-.- 0 9 0 0 2 0 5 1 9 1 0 O 6 9 9 0 0 3 2 CHJEt3Ph ratio 20/80...- Film still tacky a ter 11 c ays C HdEt3Phratio80/20...- OlllOll 0'4'0 4|0I4|7|0|0|0 6 0 6 3 0 TABLE xiv The nature of the present invention having thus been described, what is claimed as new and useful and desired to be secured by Letters Patent is: E m tNo A B c D xpm en 1. A process of preparing a synthetic resin Reshkmm dime] 60/40. which comprises mixing a major proportion of a d1u' eueinfecd. benzene hydrocarbon free from olefimc unsatuvarnlishtggeeparationl ARLO ration with a minor proportion of a conjugated Length, g diolefin of 4 to 6 carbon atoms, cooling the mix- 335 ture to a temperature between 0 C. and 40 0., Base loss, percent. at that temperature gradually adding to the mix- 3533;; M1 mhai ture a solution of aluminum chloride dissolved Color- 19-11. in a low freezing, inert, non-complex forming fflggggy i solvent in a-concentration between about 2 and Air driod'film 1 5 3.5 g./100 cc., also adding to the reaction mixt ggfif i 8: ture additional diolefin incrementally during the grease resistance course of the reaction until the ratio of total dioleigfigggggffggfj; fin to aromatic hydrocarbon reaches a value be- H s o res taoccfln 0. tween 50/50 and 75/25, and separating the rea g g sulting hard resin from the reaction mixture.

g i t 2. A process according to claim 1 wherein the oitiiiciiii iiiigj oj benzene hydrocarbon is toluene. gloxrosi t toccu '3. A process of preparing a synthetic resin ance'm which comprises mixing a. conjugated diolefin of ao Film fi t d;Q Fi1mf i1 4 to 6 carbon atoms with an aromatic hydrocarbon having 1 to 4 alkyl radicals as the sole sub- X 16 stituents which contain a total or 1 to 6 carbon The resms Qbtamed m Examples 11 a 12 atoms in a ratio between 50/50 and 75 25 at a were cooked with alkali refined linseed 011 and temperature between about 100 C. and 400 C. the retsultmg Var mSheS were found to have the and at that temperature adding to the mixture followmg evaluatlonsz a solution of aluminum chloride dissolved in an TABLE XV alkyl chloride of 1 to 2 carbon atoms in a 'con- Experiment Example Example centration between 0.1 and 5% to form a solid 11 12 resin. I 4; A process according to claim 3 wherein the Varnish prep: aromatic hydrocarbon is durene.

gggf g i a $1111 5. A process of preparing a synthetic resin 'rhioocrl Naphtha: Naphtha. which comprises mixing butadiene1,3 and tolu- Gargnefl one in a weight ratio between 50/50 and 60/40 olor. 12-13..... 10-11. Viscosity. 'r-U.-. ..N. 40* 1n the presence of an alkyl chloride reaction Reduced We 22 diluent having 1 to 2 carbon atoms per molecule, Air dried film: a

Hardness o cooling the mixture to a temperature between about -10 C. and -40 0., at that temperature 4. gradually adding to the mixture a solution of galuminum chloride dissolved in an alkyl chloride 0 of l to 2 carbon atoms in a concentration between about 2 and 5%, quenching the residual 0. catalyst with an alcohol at a conversion level be- 3; tween 51 and 72% based on total hydrocarbon g. reactants, driving ofi the alkyl chloride, removing the quenched catalyst residues from a solution of the resin by washing with water and removing The resins obtained in Example 14 were cooked unreacted reagents by vacuum stripping at a with alkali refined linseed oil and the resulting temperature below about 260 C. varnishes were found to have the following 6. A process according to claim 5 wherein the evaluations; alkyl chloride diluent is present in an amount TABLE XVI Varnish preparation Varnish film properties Base Gardner Red. Air dried tilm 1 Baked fllm I (00k time, 1085 cure m'mm' percent Color Vise. H W .G C F S T H W G O F s T k ll-l2U-V 2100400220001000 Z351: 11 X 22 1 4 0 o o 3 2 2 0 0 s o 4 0 5142.-. 10-118 3004000220000000 5142... 1415UV 2513330500000000 6105... 13-14 R-s 4010430100000000 5:06 11-12 N 38 2 2 0 0 7 3 0 0 0 0. 0 0 0 0 2115 9-1011 711-5240500000000 0:10 v-sr 9115090900001000 1:10 12-13R-S 3600096200000200 m3 12-13IU 4000006000000200 6:28 10-l1T-U ,3604006200000000 6:45 13-141 .4103103110000100 6:03 12R-S 3900005210000000 4:57 10-111 4103005410000000 6:54 12-131-1 8901100000000000 m2 11-12U-v 38010020000 '00000 19 equal to about one half the total volume of hydrocarbon reactants.

'7. A method for preparing a synthetic resin which comprises reacting a conjugated dioiefin of 4 to 6 carbon atoms with an aromatic hydrocarbon free from olefinic unsaturation in a ratio between 50/50 and 75/25 at a temperature below C. in the presence of a Friedel-Crafts type catalyst dissolved in a low freezing, inert, non-complex forming solvent in a concentration between about 0.1 and 8. Process according to claim 7 in whichthe aromatic hydrocarbon contains at least two alkyl side chains.

9. Process according to claim 8 in which the alkyl side chains of the aromatic hydrocarbon contain a total of at least 3 carbon atoms.

10. Process according to claim 7 in which the aromatic hydrocarbon is a naphthalene hydrocarbon.

11. Process according to claim 7 in which the aromatic hydrocarbon is an ethyl benzene.

12. Process according to claim 'I in which the aromatic hydrocarbon is durene.

13. A method of preparing a synthetic resin which comprises reacting a conjugated diolefin of 4 to 6 carbon atoms with an aromatic hydrocarbon selected from the group consisting of benzene, toluene. the xylenes, the ethyl benzenes, naphthalene, and durene in a ratio between 50/50 and 75/25 at a temperature below 0 C. in the presence of a Friedel-Crafts type catalyst dissolved in a low freezing, inert, non-complex 20 weight ratio between /50 and /40 in the presence of an alkyl chloride reaction diluent having 1 to 2 carbon atoms per molecule, coolin the mixture to a temperature between about 10 C. and 40 C., at that temperature gradually adding to the mixture 9. solution of aluminum chloride dissolved in an alkyl chloride of 1 to 2 carbon atoms in a concentration between about 2 and 5%, quenching the residual catalyst with an alcohol at a conversion level between 51 and 72% based on total hydrocarbon reactants, driving off the alkyl chloride, removing the quenched catalyst residues from a solution of the resin by washing with water and removing unreacted reagents by vacuum stripping at a temperature below about 26 C.

15. Process according to claim 14 in which the aromatic hydrocarbon is benzene.

16. Process according to claim 14 in which the aromatic hydrocarbon is naphthalene.

17. Process according to claim 14 in which the aromatic hydrocarbon is durene.

18. Process according to claim 14 in which the aromatic hydrocarbon is a xylene.

GEORGE E. SERNIUK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,947,626 Thomas Feb. 20, 1934 2,317,842 Wolfram et al Apr. 2'7, 1943 2,476,000 Sparks et al July 12, 1949 FOREIGN PATENTS Number Country Date 516,931 Great Britain Jan. 16, 1940 583,481 Great Britain Dec. 19, 1946 

1. A PROCESS OF PREPARING A SYNTHETIC RESIN WHICH COMPRISES MIXING A MAJOR PROPORTION OF A BENZENE HYDROCARBON FREE FROM OLEFINIC UNSATURATION WITH A MINOR PROPORTION OF A CONJUGATED DIOLEFIN OF 4 TO 6 CARBON ATOMS, COOLING THE MIXTURE TO A TEMPERATURE BETWEEN 0* C. AND -40 C., AT THE TEMPERATURE GRADUALLY ADDING TO THE MIXTURE A SOLUTION OF ALUMINUM CHLORIDE DISSOLVED IN A LOW FREEZING, INERT, NON-COMPLEX FORMING SOLVENT IN A CONCENTRATION BETWEEN ABOUT 2 AND 3.5 G./100 CC., ALSO ADDING TO THE REACTION MIXTURE ADDITIONAL DIOLEFIN INCREMENTALLY DURING THE COURSE OF THE REACTION UNTIL THE RATIO OF TOTAL DIOLEFIN TO AROMATIC HYDROCARBON REACHES A VALUE BETWEEN 50/50 AND 75/25, AND SEPARATING THE RESULTING HARD RESIN FROM THE REACTION MIXTURE. 